Water-soluble basic dyestuffs



Patented May 20, 1941 lVATER-SOLUBLE BASIC DYESTUFFS Gerd Kochendoerfer, Ludwigshafen on the- Rhine, Werner Mueller, Cologne, Bernd Eistert, Lu'dwigshafen on the: Rhine, and Walther Rotter, Cologne-Deutz, Germany, assignors to General Aniline & Film Corporation, a corporation of Delaware No Drawing. Application July 27, 1939, Serial No.

4 Claims.

The present invention relates to new basic dyestuffs. We have found that watersoluble basic dyestufis which are fast to light are obtained by causing 1.3.3 trialkyl-2-methylene-indolines which are substituted in 5-position by fluorine, 5 ing by their great strength and better fastness chlorine, bromine or trifluormethyl to react in to light while also having satisfactory solubility acid medium with aldehydes the aldehyde groups in water. They are eminently suitable for dyeing of which are in conjugation with a tertiary basic acetate artificial silk and they may also be used nitrogen atom by at least one carbon-carbon for dyeing paper, silk, leather and cotton mordouble linkage. danted with tannic acid. The lakes prepared Basic aldehydes of the said kind are for extherefrom by reaction with complex phosphoample para-aminobenzaldehydes the amino group tung'stic and/or phosphomolybdic acids are also of which is substituted by two identical or difdistinguished by high fastness to light. ferent alkyl, aralkyl or aryl radicles, among which The following examples will further illustrate there may be mentioned para-N-dimethylaminohow the said invention may be carried out in and para-N-diethylaminoebenzaldehyde, para-N- practice, but the invention is not restricted to omega cyanethyl N -benzylaminoben zaldehyde, these examples. The parts are by weight. para-aldehydo N alkyl-diphenylamines, e. g. Example 1 para aldehydo N methyldiphenylamine and para-aldehydo-para ethoxy-N-methyldiphenyl- A solution of 20 parts of 5-ch1or-1.3.3-tr-imethamine, and also para-dimethylamino-cinnamalyl-z-methylene-indoline and 1 Of D dehyde, and also heterocyclic nitrogen compounds hy p ah v-N-m hy ph v i substituted by the aldehyde group, such as 1- glacial acetic acid is heated for 6 hours at about methyl -2 -phenylindo1e- 3 aldehyde, 1.3.3-tri- 100 C. The reaction mixture is poured into methyl 2 methylene-indoline-omega-aldehyde 25 such an amount of hot water that the resulting and 1.2.3.3-tetramethyl-indoline-5-aldehyde. dyestufi is completely dissolved. The resinous Among suitable 5-substituted 1.3.3-trialkyl-2- lay-products are filtered off and the dyestuff methylene-indolines there may be mentioned for salted out. It dyes acetate artificial silk reddish example 5-chlor-l..3.3-trimethyl-Z-methyIene-inviolet shades of very good fastness to light from doline or the 5-chlor-1.2.3.8tetramethylindolineaqueous solution. The dyeing is capable of being methosulphate derived therefrom and the corredischarged white. ,Acetate artificial silk may sponding 5-fluor-, 5-bromand 5-trifluormethyl also be printed with the dyestuff by using the compounds or the 7-chlor or 'l-methoxy-derivausual printing pastes. 1 tives, the nitration products or also 4.7-dimeth- The dyestuil may be formulated as follows:

CH3 CH3 schaft, vol. 31, pages 1496 to149'7 (1898), from o the corresponding phenylhydrazines.

The reaction may be effected by bringing the reactants together, and if necessary moderately heating them, in glacial acetic acid, alcoholic hydrochloric acid, acetic anhydride orother acid liquid.

'In Germany July 29, 1938 (U1. 26024il) As compared with the known dyestuffs containing no substituent of the above identified group in the 5-position of the indoline ring, the new dyestuffs are distinguished generally speak- By using the equivalent amount of the 7-methoxyder-ivative instead of 5-chlor-l.3.3-trimethyl 2unethylene-indoline a somewhat more bluish A solution of l6 parts of 5-chlor-1.2.3.3- tetramethyl-indoline-methosulphate and 10 parts of para-N-diethylaminobenzaldehyde in parts oi glacial acetic. acid is heated for 3 hours at about C. Afterdilution with Water, filtration of the solution and salting outothere is obtained a;

dyestuff which dyes silk and acetate artificial silk Fries bluish red shades. If there be precipitated from a solution of the dyestufi by means of phosphotungstic acid the complex color lake, a violet pigment dyestulf having good fastness to' light is obtained.

The dyestuff may be formulated as follows:

CH3 CH3 ....=..@N...H.. a a

i CH? Similar dyestuffs are obtained under otherwise identical conditions with the following 'aldehydes:

Color of dyeing Aldehyde on acetate artificial silk ParaN-dimethylaminobenzaldehyde Bluish red. Paral-lNiomega-cyanethyl-N-ethylammo-benzal- Do.

Para-N-methyl-N-phenylamino-benzaldeliyde Violet red. Pera-N-dimethylaminocinnamaldehyde Blue.

Example 3 C CH:

g The dyestufi may also be prepared by causingthe nitro-5-chlor-L3.3-trimethyl-2-methyleneindoline set free from rthe. above mentioned nitro compound by treatment with caustic soda solue tion to react in alcoholic solution with the aldehyde with the addition of hydrochloric acid or phosphoric acid.

Example 4 21 parts of 1.3.3-trimethyl+2-methylene-indo line-omega aldehyde are heated with 22 parts of 5-chlor-13.3-trimethyl-2-methylene-indoline in '10 parts of aceticanhydride for'half arihour aft about 100 C. After diluting with Water, filtering [the solution and salting out there is obtained a dyestufi which dyes silk and cotton mordanted with tannic acid brilliant bluish red shades. I

Example 5 12 parts of 1-methyl-2 phenylindole-l -aldehyde are heated with 10-parts of 5-chlor-l.3 .3- trimethyl-2-methylene-indoline inf-; parts of glacial acetic acid for 3hours at about C. After diluting with hot water, filtering and salt ing out there is obtained a dyestuff-very fast to light which dyes weighted silk scarlet, red shades and acetate artificial silk orange-red shadesa: 71

The dyestuff corresponds to the following formula:

Similar dyestuffs are obtained by using, in-

stead of the said indoline, its '7-chlor or 7- methoxy derivatives, its 4.7-dimethoxy derivatives or the mononitro compound specified in Example 3. i

Instead of 5-chlor-l.3.3-ttrimethyl-2-methyleneeindoline there may also be used indolines containing ethyl radicles instead of one or more methyl groups.

Example 6 8.9 parts of para-N-diethylaminobenzaldehyde and 9.6 parts of 5-fluor-1.3.3-trimethyl-2-methylene-indoline are dissolved in glacial acetic acid and heated for some hours at 100 C. The solution obtained is diluted with water and the dyestuff salted out therefrom. It is redissolved in hot water, freed from resinous insoluble byproducts and again salted out. It is thus obtained in the form of crystals which are readily soluble in; alcohol or water. The dyestuff dyes cotton mordantedwith tannic acid and acetate artificial silk reddish violet shades. The complex color lake produced by means of phospho-tungsticmolybdic acid is distinguished by its purity and fastness to light.

The dyestufi may be formulated as follows:

0H. CH3

. CH=CHON(C2H5)2 G1- Similar dyestuffs are obtained under otherw se identical conditions with the following aldehydes:

By using the equivalent amount of 5-brom- 1.3.3-trimethyl-2-methylene-indoline instead of the 5-fiuor-.1.3.3-trimethyl-2-methylene-indoline the following dyestuffs may be prepared:

5-brom-l.3.3-trimethyl 2-methylene-indolino 0f yeing V on acetate I h artillcialsllk Para-N-diethylaminobenzaldehyde Reddish violet. Paraaldeliydo-para-ethoxy-N-methyldiphenyl- Do.

amine. a Pairadbg-omega-cyanethyl-N-ethylaminobenzel- Bluish pink.

9 y Para-N diethylamino-cinnamaldehyde Blue. lilruaiethyl 2 methylene indoline omega Bluish pink.

e y e. l-methy l-z -phenyl-indoledaldehyde Orange.

By using the equivalent amount of B-trifluormethyl-1.3.3-trimethyl-2-methylene-indoline instead of the fluor-1.3.8-trimethyl-2-methylene indoline the following dyestuffs may be prepared:

. Color of dvein" a-tnfluormethyl 143.3 -tr1methyl 2 methylene indoline condensed with on i 1 cial silk Para-pldehydo-para-ethcxy-r -methyldiphenyl- Violet.

amine. 1-1nethyl-2-phenylindQIeB-aIdehyde Orange.

What we claim is: 1. Watersoluble basic dyestuffs corresponding to the general formula wherein Ph stands for a phenylene radical substituted in 5-position by a member of the group consisting of fluorine, chlorine, bromine and trifiuormethyl, wherein the Rs stand for alkyl radicals, and wherein B stands for an N-alkyldiphenylamine radical attached to the methine group shown in 4-position with reference to the amino group in l-position, and wherein X stands for the anion of an acid.

2. Watersoluble basic dyestuffs corresponding to the general formula wherein Ph stands for a phenylene radical which is substitulted in the 5-position by a member of the group consisting of fluorine, chlorine, bromine and rtrifiuormethyl, and wherein X stands for the anion of an acid.

3. The Watersoluble dyestuff corresponding to the formula (L1H? wherein X stands for the anion of an acid.

4. The watersoluble dyestuif corresponding to the formula BERND EIS'I'ERT. WALTHER RE'I'IER. 

